1. Field of the Invention
This invention relates generally to time-temperature integrating indicator devices and thermal exposure monitors, and more particularly to threshold calorimeter/shelf life monitors having a thermally moderating housing containing a liquid solution and one or more low melting point solids all correlated relative to one another and calibrated to closely match a thermal decay profile (time-temperature profile) of a perishable product being monitored and indicate, by a change in color, electrical capacitance and/or impedance, transmitted RF signals, or combination thereof, the cumulative thermal history of the product while in transit or storage and whether its time-temperature profile has been violated to a detrimental extent or if a significant amount of shelf life has been consumed.
2. Background Art
As used herein, “product” or “perishable product” is the thing or medium that is being monitored and may include food products, non-food products, medical products, drugs, research reagents, pharmaceuticals, human organs, tissues, or other substance or device that may be subject to deterioration upon exposure to thermal differences over time, or the product package. “Temperature” of the product is the measurement of the average energy of its molecules. “Heat energy” is a function of time and temperature difference. “Absorbed Heat” in a product is the total kinetic energy of its molecules. “Specific heat” is the quantity of heat needed to raise the temperature of one gram of a substance one degree Celsius. “Heat of fusion” is the quantity of heat needed to change one gram of a solid into a liquid at a constant temperature. “Heat of solution” is the amount of energy (heat) given off (or absorbed) in the dissolving of a solid into a liquid. “Melting point” is the temperature at which a solid substance changes to a liquid state. “Solubility” is the ability of a substance to form a solution with another substance. “Dissolution” is the ability of one substance to become part of another substance.
“Threshold temperature” is the temperature at which deterioration of a product begins or substantially increases based on a time and temperature thermal deterioration profile of that particular product. “Preferred storage temperature range” is a known practical temperature range within which a product must be maintained to minimize deterioration. “Thermal capacity” is defined as the product of specific heat, volume and density of a material. “Thermal conductivity” is the amount of heat energy conducted through a cubic meter of a material per second when the temperature difference between opposite faces of the cube is one degree Celsius. “Cold Soak” is exposure of a device to a temperature for an amount of time sufficient for the entire device to be uniform at the exposure temperature.
A “temperature sensitive” product does not decay or become spoiled as a result of exposure to a given temperature; instead, it spoils due to the amount of heat imparted to it as a result of a temperature difference over time. In other words, a given product, such as a food product or produce, can safely tolerate short exposures to an elevated temperature, but not long exposures. Thus, prior art devices that merely indicate that a temperature threshold was achieved or exceeded at some point in time do not indicate the cumulative amount of heat energy absorbed within a preferred storage temperature range and whether, at any time, the cumulative heat energy absorbed has taken place for a period of time sufficient to cause any degree of deterioration based on the time and temperature thermal deterioration profile of the perishable product.
It is of utmost importance to maintain processed produce such as food products and perishable non-food products such as medical products, drugs, research reagents, pharmaceuticals, human organs and tissues, etc., within a predetermined temperature range and to determine whether such products may have been exposed to detrimental temperatures outside of a specified temperature range over time during some step in the chain of distribution from the source to the destination.
The demand for processed produce and perishable non-food products has pushed the limits of the distribution systems of the perishable products industry to maintain an unbroken temperature controlled chain from field to consumer and industry. Many segments of the food industry utilize a Hazard Analysis and Critical Control Point system (HACCP), which is a world-recognized, common sense approach to food safety and prevention of food contamination.
The HACCP has outlined seven principles for food safety and prevention of food contamination: (1) Conduct a hazard analysis to identify potential hazards that could occur in the food production process; (2) Identify the critical control points (CCPs)—those points in the process where the potential hazards could occur and can be prevented and/or controlled; (3) Establish critical limits for preventive measures associated with each CCP; (4) Monitor each CCP to ensure it stays within the limits; (5) Take corrective actions when monitoring determines a CCP is not within the established limits; (6) Keep records that document the HACCP system is monitored and working correctly; and (7) Verify that the HACCP system is working properly through tests and other measures.
Existing HACCP programs in place at the processing end of the chain are not equipped with proper tools to monitor all of the critical control points (CCP's) in the cold chain, and temperature related problems can still occur throughout the distribution chain. Thus, there is a need for a device that can be used for economically monitoring the links in the cold chain, especially when perishable loads are broken up and re-distributed.
Time-temperature integrating indicator devices and thermal exposure monitors are known in the art, most of which rely on diffusion with respect to temperature, the rate of reaction of chemical components with respect to temperature, enzymatic reactions with respect to temperature, or viscosity with respect to temperature, to produce a response emulating a given thermal deterioration profile. Indicating devices utilizing radio frequency (RF) transponder technology are also known in the art, which receive an incoming interrogation signal and respond thereto by generating and transmitting an outgoing responsive signal which is modulated or otherwise encoded so as to uniquely identify or label the particular object to which the transponder element is affixed.
Our previous U.S. Pat. No. 6,425,343 and pending application Ser. No. 10/201,385 and Ser. No. 10/816,974, which are hereby incorporated by reference herein in their entirety, disclose cumulative thermal exposure monitors that utilize shape memory alloy technology. These devices have a have a thermally-conductive housing adapted to be placed in close proximity to a product to be monitored and at least one thermally-responsive shape memory alloy member in the housing that has a first shape at temperatures below a critical temperature and a second shape at temperatures above the critical temperature and a transformation temperature range encompassing a prescribed time-temperature profile which is determined by the detrimental temperature related to the product being monitored. A visual indicator associated with the thermally-responsive member is moved from an initial position as the thermally-responsive member changes from the first shape to the second shape to visually indicate whether the product being monitored has been exposed to temperatures above the prescribed detrimental temperature for a period of time that would be detrimental to the product. The data may also be retrieved remotely via RF transponder technology without directly viewing the monitor device. The present invention differs in structure and operation from the previous patents and applications.
Spevacek, U.S. Pat. No. 6,614,728 discloses a time-temperature integrating indicator having an amorphous material in operable contact with a porous matrix, wherein the amorphous material only migrates into the porous matrix at or above a predetermined temperature. Use of the invention simplifies monitoring of the cumulative temperature exposure of the product because no additional actuation step is required. The indicator is especially useful in monitoring the cumulative time-temperature exposure of a perishable product for a short period of time at an abusive temperature.
Qiu, et al, U.S. Pat. No. 6,435,128 discloses a time-temperature indicator device that provides a visually observable indication of the cumulative thermal exposure of an object. The device includes a substrate having a diffusely light-reflective porous matrix and a backing. The backing includes on its surface a viscoelastic indicator material for contacting the substrate and a barrier material for substantially inhibiting the lateral and longitudinal flow of viscoelastic indicator material between the substrate and the backing.
Prusik, et al, U.S. Pat. No. 6,544,925 discloses an activatable time-temperature indicator system useful in tracking the thermal exposure history of a temperature-sensitive perishable product and providing a visually-distinct signal, such as a change in color density, at the expiration of a predetermined time-temperature integral comprises a first element, such as a direct thermal printing label, comprising a composition having at least a first co-reactant of a color-forming reaction. A second, activator element, such as an adhesive tab capable of being affixed to the label element, comprises an activator component, such as a second co-reactant of the color-forming reaction or a solubilizing agent for prompting the interaction of the co-reactants of the label composition. The activator tab element is affixed to the label composition to activate for reaction at ambient conditions the normally high-temperature color-forming composition of the label at about the same time as the label is affixed to the perishable product. Such an ability to effect the initiation of the indicator reaction at a given time eliminates any unknown, premature color formation in the indicator system to thereby ensure a true time-temperature history of the perishable product.
Roth, U.S. Pat. No. 6,524,000 discloses time-temperature indicators activated with direct thermal printing and methods for their production. Recording materials are converted in a direct thermal imaging apparatus to time temperature indicators by exposure to heat from the thermal print head of a direct thermal printer. Methods for converting a recording material to a time temperature indicator comprise heating the recording material with a direct thermal imaging apparatus. The recording material contains an indicator compound which is convertible from an inactive state to an active state when heat is applied thereto by a direct thermal imaging apparatus for less than one second. Time-temperature indicators with active indicator compounds in a printed pattern are formed by a direct thermal imaging apparatus.
Prusik, et al, U.S. Pat. No. 6,042,264 discloses a time-temperature indicator label for measuring the length of time to which a product has been exposed to a temperature above a pre-determined temperature. The period of time of exposure is integrated with the temperature to which the indicator is exposed. The label is a composite of a plurality of layers adapted to be adhered at its underside to a product container. The label includes a printable surface layer, a longitudinal wicking strip that is adhered underneath the surface layer substantially at the opposite extremities only of the wicking strip and a lower substrate layer forming an envelope with said surface layer. A heat-fusible substance, which melts and flows above a pre-determined temperature, is applied on the surface of the wicking strip contiguous to at least one of the ends of the wicking member. When the heat-fusible substance is exposed to a temperature above the pre-determined temperature, the heat-fusible substance flows along the length of the wicking member. The label has a printable surface layer and is sealed at its peripheral edge to the peripheral edge of the substrate layer. These layers encapsulate the wicking member and the heat-fusible substance. The surface layer is provided with a sight window at an intermediate location over the wicking member through which the progress of flow on the wicking member is observed.
Ezrielev, et al, U.S. Pat. No. 5,476,792 discloses a time-temperature indicator device for recording the duration of time over which a temperature has been established above a predetermined temperature, which includes a dye-compatible polymer composition having a softening point above the predetermined temperature and a polymer-compatible dye composition in contact with the polymer composition and present in a quantity with respect to the polymer composition sufficient for diffusion through the polymer composition whenever the polymer composition is above the predetermined temperature. The quantity is selected so that the extent of diffusion corresponds to the duration of exposure above the predetermined temperature relative to the total time required for substantially complete diffusion. Articles for which a heat history above a predetermined temperature is to be recorded, in combination with the disclosed time-temperature indicator devices are also described. Methods for recording a duration of time over which a temperature has been established above a predetermined temperature utilizing the disclosed time-temperature indicator devices are also discussed.
Patel, U.S. Pat. No. 5,254,473 discloses an indicator composition and process capable of changing color in relationship to its exposure to a temperature above and below a base line temperature and to the time of said exposure, for monitoring the time-temperature history of a substrate, depositable as a layer on said substrate, comprising a dispersion of either a binder comprising a reaction inert, neutral finely divided absorbent, in the presence of a reactant comprising a salt of an acid or an organic compound substituted by at least one moiety which, in ionic form, is an anion or a binder/reactant, comprising at least one solid organic polymer whose constituent units contain, as a covalent substituent, at least one moiety which, in ionic form, is an anion; as indicator, at least one acid sensitive pH dye and as activator, at least one base. This composition and process may be utilized to form a solid state device for monitoring integral values of time and temperature during storage of perishables. The device is a single solid indicating layer deposited upon a substrate. The time required for the color change and the activation energy of the device can be varied by varying the concentration and nature of reactants, catalysts, additives and polymeric binder/reactant matrix. The color change can be gradual or abrupt and exhibited as a continuous strip, as alphanumeric symbol(s) or as a line array that can be read by a bar code reader.
Jalinski, U.S. Pat. No. 5,182,212 discloses a new and improved integrating indicator system operable to signal the attainment of one or more preselected time-temperature integrals which monitor the temperature and time history of a product utilizing a dual system of specific reaction pairs which simultaneously generate acid and alkali from two neutral substrates. One of the substrates is present in excess of the other. The preferred dynamic indicator system generates a constant pH buffer in the alkali range that is maintained until one of the substrates is depleted. At that time, a rapid pH change in the indicator solution to the acid range occurs, resulting in a very sharp visual color change in a pH-sensitive dye. In preferred embodiments, the specific reaction pairs are enzyme/substrate pairs, preferably urease/urea and yeast/triacetin. A preferred combination pH-sensitive dye package includes m-nitrophenol, p-nitrophenol and litmus to provide an indicator which changes from green to reddish pink upon the expiration of a given amount of time at constant temperature, or in a shorter period of time, upon exposure to elevated abuse temperatures. In especially preferred embodiments, one of the enzyme substrate pairs includes an enzyme component provided by a microorganism which has been shock treated prior to incorporation in the indicator to improve temperature sensitivity and provide extended half life. The new and improved integratin indicators are adapted for use with packaged foodstuffs intended for refrigerated and room temperature handling and storage at temperatures between about 20° F. to about 120° F.
Patel, U.S. Pat. No. 5,053,339 discloses a color changing device for monitoring the time-temperature storage history, i.e. shelf life, of perishable products. The device is constructed of an activator tape, containing an activator composition matrix, an indicating tape, containing an indicating composition matrix and an optional barrier matrix between the activator tape and the indicating tape. At least one matrix is a pressure sensitive adhesive. The activating composition, e.g. an organic acid such as citric acid, diffuses through the barrier and/or indicating matrix to continuously contact the indicating composition, e.g. an acid-base dye indicator such as 2,2,4,4′,4″,-pentamethoxy triphenylmethanol, to produce a visually observable color change at the temperature being monitored. The color intensifies with time and temperature, as more activator composition diffuses into the indicating matrix. The matrices are water-impermeable and the device preferably possesses activation energy and rate constant values for the color change, which are substantially the same as those for product decay. This allows accurate and continuously observable monitoring of the available shelf-life of the perishable product to which the device is adhered to.
Patel, U.S. Pat. No. 5,045,283 discloses a moving boundary device for monitoring the time-temperature storage history, i.e. shelf life, of perishable products. The device is constructed of an activator tape, containing an activator composition in an activator matrix, an indicating tape, containing an indicating composition in an indicator matrix in which the matrices are adhered together to form a wedge-shaped composite matrix, preferably by means of a pressure sensitive adhesive. The device operates by allowing the activating composition, e.g. an organic acid such as citric acid, to diffuse through the increasingly thicker composite matrix to continuously contact the indicating composition, e.g. an acid-base dye indicator such as 2,2′,4,4′,4″,-pentamethoxy triphenylmethanol, to produce a visually observable color change at the temperature being monitored. The color change appears as a moving boundary at the color/non-color interface which moves transversely along the length of the device toward the thicker end of the composite matrix. The matrices are water-impermeable and the device preferably possesses activation energy and rate constant values for the color change which are substantially the same as those for product decay. This allows accurate and continuously observable monitoring of the available shelf-life of the perishable product to which the device is adhered.
Preziosi, et al, U.S. Pat. No. 4,892,677 discloses a process for producing articles (defrost indicators) useful for monitoring the time-temperature history of perishable items. The process initially involves forming a solution comprised of a diacetylenic monomer and a solvent. The solution is frozen, and the frozen solution having crystalline diacetylenic monomer therein is irradiated to partially polymerize the diacetylenic monomer. Partial polymerization of the crystalline diacetylenic monomer admixed with frozen solvent results in the production of a novel article of manufacture having color. The novel article of manufacture is comprised of frozen solvent, diacetylenic monomer, and colored polydiacetylene. Due to the intensity of the color of the polydiacetylene, the entire article of manufacture appears to be colored. The colored article of manufacture may be attached to various perishables to monitor the shelf life of the perishables. upon exposure to temperatures above a critical temperature, the frozen solvent melts and extracts unreached monomer from the colored polymer, thereby causing a sharp color transition which indicates that the perishable should possibly be discarded.
Bradley, U.S. Pat. No. 4,292,916 discloses disposable timer and product storage condition tape indicator in which components of a carrier mixture react physically and/or chemically with one or more receptive layers. The carrier mixture and receptive layers are so comprised as to react during a given time interval, the interval being dependent upon and constantly modified by such external physical conditions as temperature, moisture, light, radiation, or pressure. During the timing period the device can either give a changing color display which is matched in rate to the declining freshness of a food or medicine in a container to which the device is attached or can cause the appearance or disappearance of words or symbols or sticky areas or odors. A variety of means for activating the timer are possible.
Kydonieus, et al, U.S. Pat. No. 4,212,153 discloses a laminated time color indicator which changes in a visually perceptible mode with the passage of time and a method for making such an indicator. At least two layers are provided whereby the molecular migration of an agent in an interior layer to the outermost surface of the exterior layer causes a change which can be visually perceived, e.g., a change in color or shade. Preferred embodiments include the migration of a dye or the migration of an acid or base wherein the outermost layer has the other member of an acid-base pair and a pH indicator.
Giezen, et al, U.S. Pat. No. 4,154,107 discloses a time temperature device utilizing an activator acid in a pressure sensitive adhesive which migrates to contact an organic dye to produce an aqueous-mediated color change. The preferred device also requires an absorbent paper element to contain the indicator and a wetting agent to retain water to introduce color change. The activating and indicating components used in the device are water-soluble and hence the performance of the device is adversely affected by moisture and humidity. In order to protect the device, an enveloping plastic film is employed.
Witonsky, U.S. Pat. No. 3,942,467 discloses a system operable to signal the attainment of one or more preselected time-temperature integrals which monitor the temperature history of a product utilizes an organic compound which is subject to solvolysis with the generation of an acid, at least one base in an amount less than the stoichiometric equivalent of the acid generated, and a pH sensitive indicator.
Myers, U.S. Pat. No. 3,520,124 discloses a device that indicates a predetermined time interval based on two or more materials that react, either chemically or physically over a predetermined period to produce a termination signal. The reacting materials are carried on a base member and are separated by a barrier preventing contact. Upon elimination of the barrier, a commencement signal is produced indicating the time reaction is underway.
Transponder or transceiver type identification systems are also known in the art, and generally are capable of receiving an incoming interrogation signal and responding thereto by generating and transmitting an outgoing responsive signal. The outgoing responsive signal, in turn, is modulated or otherwise encoded so as to uniquely identify or label the particular object to which the transponder element is affixed.
Blama, U.S. Pat. RE 37,956, which is hereby incorporated by reference herein in its entirety, discloses a method and apparatus for identifying an item to or with which a radio frequency identification tag is attached or associated. The tag is made of a nonconductive material having a flat surface on which a plurality of circuits are pressed, stamped, etched or otherwise positioned. Each circuit has a capacitance and an inductance. The capacitance is formed from the capacitive value of a single capacitor. The inductance is formed from the inductive value of a single inductor coil having two conductive ends each connected to the capacitor. Each tag is associated with a binary number established from a pattern of binary ones and zeros, which depend on the resonance, or nonresonance of each circuit, respectively, and the circuits position with respect to the binary table. The binary number may be converted to a decimal number using a binary table for conversion.
Mehregany, et al, U.S. Pat. No. 5,712,609, which is hereby incorporated by reference herein in its entirety, discloses a micromechanical memory sensor. The sensor comprises a latch member mechanically latching upon detection of a threshold value of a variable condition and circuitry for detecting such latching. The sensor further includes a resetting mechanism for electrically unlatching the latch member whereby the sensor latched purely mechanically is electrically reset for repeat use. The sensor is capable of maximum temperature measurement (polling) by an external RF signal provided by a “reader”, the transponder transmits tire identification and tire pressure data in digitally-coded form. The transponder is “passive” in that it is not self-powered, but rather obtains its operating power from the externally-provided RF signal. The tire has two spaced beads, each including an annular tensile member of wound or cabled steel wire. The transponder antenna is positioned adjacent one of the annular tensile members for electric or magnetic field coupling to the annular tensile member.
Geschke, et al, U.S. Pat. No. 5,661,651, which is hereby incorporated by reference herein in its entirety, discloses a wireless system for monitoring vehicle parameters, such as tire pressure, using radio frequency (RF) signals transmitted from transmitters close in proximity to an associated parameter sensor, to a centrally located receiver. The transmitted RF signals from the transmitters may be distinguished by the frequency of the respective transmitted RF signals. To detect the presence of an RF signal having a particular frequency, the wireless vehicle parameter monitoring system of one embodiment includes a digitally controlled tuner or a plurality of parallel bandpass filters, which pass different ranges of frequencies corresponding to the frequencies of the RF signals output from the transmitters. In this manner, RF signals transmitted from different tires may be distinguished based upon the frequency of the transmitted signal. The receiver of this system may be implemented in the receiver of a trainable transmitter such that a dedicated receiver need not be provided.
Schuermann, U.S. Pat. No. 5,451,959, which is hereby incorporated by reference herein in its entirety, discloses a transponder system comprising an interrogation unit for communicating with a plurality of responder units. The responder unit contains a parallel resonant circuit having a coil and a capacitor for reception of a RF interrogation pulse. Connected to the parallel resonant circuit is a capacitor serving as an energy accumulator. A processor may be provided for receiving input signals from a sensor which responds to physical parameters in the environment of the responder unit, for example to the ambient temperature, the ambient pressure or the like. The sensor could for example be an air-pressure sensitive sensor. In this case the responder unit can be installed in the carcass of a vehicle pneumatic tire and, with the aid of an interrogation unit contained in the vehicle, it is possible to continuously monitor the air pressure in the tire.
Dunn, et al, U.S. Pat. No. 4,911,217, which is hereby incorporated by reference herein in its entirety, discloses a combination pneumatic tire and integrated circuit transponder for tire identification wherein the transponder has two electrodes, a first of which is positioned such that the average spacing of the first electrode's surface from one of the tire's steel reinforcing components, such as an annular tensile member in its bead or a steel-reinforced ply, is substantially less than the average spacing of the second electrode's surface from the reinforcing component. The transponder located within the tire structure is capable of transmitting an identifying digital signal in response to interrogation by an R/F electric field emanating from outside the tire.
Carroll, U.S. Pat. No. 4,857,893, which is hereby incorporated by reference herein in its entirety, discloses a transponder device that receives a carrier signal from an interrogator unit which is rectified by a rectifying circuit in order to generate operating power. Logic/timing circuits derive a clock signal and second carrier signal from the received carrier signal. This clock signal reads a unique identifying data word from a programmable read only memory (PROM). The data word is encoded and mixed with the carrier signal in a balanced modulator circuit. The output of the balanced modulator is transmitted to the interrogator unit where it is decoded and used as an identifying signal. The identifying signal identifies the particular transponder device from which it originated. The rectifier and balanced modulator circuits are realized from the same diode elements. All electrical circuits of the transponder device are realized on the same monolithic semiconductor chip, and in one embodiment, an antenna receiving/transmitting coil is also part of the chip, being placed around the periphery thereof.
Galasko, et al, U.S. Pat. No. 4,578,992, which is hereby incorporated by reference herein in its entirety, discloses a tire pressure indicating device including a coil and a pressure-sensitive capacitor forming a passive oscillatory circuit having a natural resonant frequency which varies with tire pressure due to changes caused to the capacitance value of the capacitor. The circuit is energized by pulses supplied by a coil positioned outside the tire and secured to the vehicle, and the natural frequency of the passive oscillatory circuit is detected. The natural frequency of the coil/capacitor circuit is indicative of the pressure on the pressure-sensitive capacitor.